JPS6225641B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to compositions for protecting cultivated plants from the phytotoxic effects of herbicides. In the present invention, the phenylpyrimidine represented by the following formula is applied to the planted area of cultivated plants at the same time as the application of the herbicide or immediately after the application of the herbicide, or the phenylpyrimidine represented by the formula is contained together with the herbicide. A composition is applied to the cropland.
The present invention also relates to compositions containing phenylpyrimidines of the formula: The phenylpyrimidine of the present invention has the following formula: (In the formula, n represents an integer of 0, 1, 2 or 3, R ₁ and R ₃ each independently represent a halogen atom, R ₂ represents a hydrogen atom, R is a halogen atom, a nitro group, Cyano group, -
XR ₅ , ―NR ₆ R ₇ , ―CO―R ₄ , ―CONR ₆ R ₇ , ―
SO ₂ --NR ₆ R ₇ , --SO ₃ H, unsubstituted or halogen atom, --OR ₅ , --NR ₆ R ₇ , --CO--R ₄ or alkyl having 1 to 6 carbon atoms substituted with cyano group, represents a cycloalkyl group having 3 to 6 carbon atoms, an unsubstituted or halogen-substituted alkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms; R ₄ represents a hydrogen atom, an unsubstituted or halogen atom-substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms, and R ₅ is represents the same meaning as R ₄ and additionally represents an alkylcarbonyl group having 1 to 6 carbon atoms, R ₆ and R ₇ each independently represent a hydrogen atom or an alkenyl group having 3 to 6 carbon atoms, or either R ₆ and R ₇ is - CO
-R ₄ or -OR ₄ group or -CONR ₆ R ₇ group, X is oxygen atom, sulfur atom, -SO- or -
SO ₂ - represents. ). Phenylpyrimidines of the formula do not exhibit a particularly selective action or do not have a sufficiently selective action by aggressive pesticides, i.e. not only against the weeds to be controlled but also against cultivated plants. A wide range of chemical compounds that cause more or less damage to
haloacetanilide, halofenochiacetate,
Cultivated plants, such as sorghum, rice, maize, cereals (wheat, rye, Ideal for protecting crops (barley, oats), cotton, sugar beet, and sugar cane. The present invention also relates to compositions containing phenylpyrimidines of these formulas together with herbicides. Useful compounds of the formula are particularly those in which n represents an integer of 0, 1, 2 or 3, and R is a halogen atom, a cyano group, a nitro group, a hydroxyl group or each unsubstituted or halogen atom,
C1-C6 alkoxy, C2-C12 alkoxyalkyl, C1-6 alkylcarbonyl, C1-6 alkylcarbonyloxy, C1-6 an alkoxycarbonyl group,
C2-C6 alkenylcarbonyl group, C2-C6 alkynylcarbonyl group, di(C1-C6)alkylamino group, C1-C6 alkylenedioxy group, phosphonyl group or represents a C1-C6 alkyl group substituted with a C1-C6 alkylphosphonyl group, a C1-C6 alkoxy group, or a C1-C6 alkylthio group, or represents an alkenyl group having 2 to 6 atoms, an alkenyloxy group having 2 to 6 carbon atoms, a formyl group or a carboxyl group having 1 to 6 carbon atoms;
an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an amino group,
5 to 6 bonded via a di(C1 to C6) alkylamino group or via a nitrogen atom
a carbonyl or carbonyloxy group substituted with a saturated heterocyclic ring, or an unsubstituted or C 1 -C 6 alkyl group;
represents an amino group substituted with an alkoxy group having 1 to 6 carbon atoms or an alkylcarbonyl group having 1 to 6 carbon atoms, or is unsubstituted or an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; represents a ureido group substituted with an alkoxy group, R ₁ and R ₃ each independently represent a halogen atom, and R ₂ represents a hydrogen atom. A particularly suitable antidote is the following formula b: (In the formula, n, R, R ₁ and R ₃ are the above general,
and particularly expresses a more limited meaning. ) Important compounds are those in which n represents an integer of 0, 1, 2 or 3, and R is a halogen atom, a cyano group, a hydroxyl group, a mercapto group, each unsubstituted or a halogen atom or an alkoxy group having 1 to 6 carbon atoms. Substituted C1-C6 alkyl, C1-C6 alkoxy or C1-C6 alkylthio; C2-C6 alkenyl, C2-C6 alkynyl , C3 -C6 cycloalkyl; carboxyl, formyl, amino; carbamoyl; or C1 -C6 alkylcarbonyl, C1 -C6 alkylamino, di(carbon represents an alkylamino group (having 1 to 6 atoms), a di(having 1 to 6 carbon atoms) alkylcarbamoyl group; or two adjacent groups R each having 1 to 6 carbon atoms;
forms an alkylenedioxy group, and R ₁ and R ₃ each independently represent a halogen atom. The most effective of these compounds are those in which each of R ₁ and R ₃ represents a halogen atom, especially a chlorine atom, and R is in the meta or para position to the pyrimidine ring. Various compounds which can specifically antagonize the harmful effects of herbicides on cultivated plants are used as safeners or antidotes.
That is, it has already been proposed as a compound that protects cultivated plants without significantly affecting the herbicidal effect on weeds to be controlled.
Due to their properties, these antidotes, or protectants, as they are known, can be used as a pre-treatment of seeds of cultivated plants (dressing seeds or seedlings) or before sowing in cultivated fields, or together with herbicides. It can be used as a tank mixture before or after plant germination. For example, British Patent No. 12277557 describes certain esters and amides of oxamidic acid to protect against attack by N-methoxymethyl-2',6'-diethyl-chloroacetanilide (Alachlor). The treatment of wheat and sorghum seeds and seedlings is disclosed. Other publications (German Patent Publications Nos. 1952910 and 2245471 and French Patent No. 2021611) describe treatments for grain, corn and rice seeds for protection against attack by thiocarbamates as herbicides. Antidotes have been proposed. DE 1576676 and US Pat. No. 3,131,509 suggest hydroxyaminoacetanilides and hydantoins for the protection of cereal seeds against carbamates, such as IPC, CIPC, etc. However, all of these preparations are unsatisfactory and no progress has been seen. Surprisingly, phenylpyrimidines of the formula are susceptible to a wide range of chemical compounds that are not or poorly tolerated by aggressive pesticides, especially by cultivated plants, such as chloroacetanilides, chloroacetanilides, carbamates, etc. and cultivated plants from attack with herbicides belonging to thiocarbamates, diphenyl ethers and nitrodiphenyl ethers, benzoic acid derivatives, triazines and triazinones, phenylureas, nitroanilines, oxydiazolones, pyridyloxyphenoxy derivatives, phosphates and pyrazoles It has the property of protecting The phenylpyrimidines of the invention preferably protect herbicides belonging to the chloroacetanilide, chloroacetamide, thiocarbamate and phosphate class of compounds. Depending on the purpose, the protectant or antidote of the formula can be used as a pre-treatment of the seeds of cultivated plants or by incorporation into the soil before or after sowing, or else before or after germination of the plants. It can be used alone or in combination with herbicides. Treatment of plants or seeds can therefore be carried out independently of the time of application of the phytotoxic chemicals. However, the treatment can also be carried out simultaneously (tank mixture). Pre-emergence treatment includes both treatment of the cropped area before sowing (ppi = pre-plant contamination) and treatment of the sown cropped area where the plants have not germinated. The application ratio of antidote to herbicide used varies depending on the mode of application. Whether the field is treated with a tank mixture or where the herbicide and antidote are applied separately, the ratio of antidote to herbicide is usually 1:100 to 10:1, preferably 1:5. to 8:1, optimally 1:1. However, if seed dressing or similar protection measures are employed, the amount of antidote may be lower, for example for a later applied amount of herbicide per hectare of cropped area. When dressing seeds, 1 kg of seeds
usually 0.1 to 10 g of antidote per person, preferably 1
~2g is required. When the antidote is applied by soaking the seeds before sowing, for example, 1-10000 ppm of active ingredient is preferably added.
Antidote solutions containing concentrations of 100-1000 ppm are used. Protective measures, such as seed dressing with antidotes of the formula and subsequent field treatment with pesticides, are usually carried out at considerable intervals. Pretreated seeds and plants can be used in agriculture,
Can overcome subsequent different chemicals in horticulture and forestry. The invention therefore relates to plant protection compositions which contain as active ingredient an antidote of the formula as well as customary carriers. As desired,
The composition may be further mixed with chemicals, such as herbicides, which act towards a favorable protective effect on the cultivated plants. Cultivated plants within the scope of the invention can be cultivated in various forms (seeds,
All plants that can be harvested (roots, stems, tubers, leaves, flowers) and from which extracts (oils, sugars, starches, proteins) can be obtained and that are cultivated and cared for for this purpose. These plants include, for example, all types of cereals, such as wheat, rye, barley and oats, and in particular rice, sorghum, cotton, sugar beet, sugar cane, soybeans, beans and peas. This antidote could be applied wherever it is desired to protect cultivated plants from the phytotoxicity of chemicals. The following compounds are listed as examples of herbicides whose action it is desirable to protect cultivated plants: Chloroacetanilide: 2-chloro-2',6'-diethyl-N-(2''-propoxyethyl)acetanilide (propachlor (Propachlor)], 2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)-aceto-o-toluidide [Metolachlor], 2-chloro-2',6 '-Diethyl-N-(butoxymethyl)acetanilide [Butachlor], 2-chloro-6'-
Ethyl-N-(ethoxymethyl)aceto-o-toluidide [Acetochlor], 2-
Chlor-6′-ethyl-N-(2″-propoxy-
1″-methylethyl)aceto-o-toluidide, 2
-Chloro-2',6'-dimethyl-N-(2''-methoxy-1''-methylethyl)acetanilide, 2-chloro-2',6'-dimethyl-N-(2''-methoxyethyl)acetanilide [ Dimethachlor], 2-chloro-2',6'-diethyl-N-(pyrazol-1-ylmethyl)acetanilide, 2-chloro-6'-ethyl-N-(pyrazol-1-ylmethyl)acetanilide -Toluidide, 2-chloro-6'-ethyl-N-(3,5-dimethylpyrazol-1-ylmethyl)acet-o
-Toluidide, 2-chloro-6'-ethyl-N-
(2″-butoxy-1″-methylethyl)acet-o
-Toluidide [Metazolachlor], 2-chloro-6'-ethyl-N
-(2″-butoxy-1″-(methylethyl)aceto-o-toluidide, 2-chloro-2′-trimethylsilyl-N-(butoxymethyl)-acetanilide, 2-chloro-2′,6′-diethyl- N-(methoxymethyl)acetanilide [Alachlor] and 2-chloro-2',6'-diethyl-N-(ethoxycarbonylmethyl)acetanilide; Chloroacetamide: N-[1-isopropyl-
2-methylpropylene-1-yl(1)〕-N-
(2'-methoxyethyl)-chloroacetamide; carbamate and thiocarbamate: N(3',
4'-dichlorophenyl)-propionanilide [Propanil], S-4-chlorobenzyl-diethyl-thiocarbamate [Thiobencarb], S-ethyl-N,N-hexamethylene-thiocarbamate [molinate] (Molinate)], S-ethyl-dipropyl-thiocarbamate [EPTC], N,N-di-sec-butyl-S-benzyl-thiocarbamate [Drepamon], S-(2,3-dichloroallyl) -diisopropylthiocarbamate and S
(2,3,3-thiochloroallyl)-diisopropylthiocarbamate [di- and trialate (-allate)], 1-(propylthiocarbonyl)-
Decahydroquinaldine, S-4-benzyldiethyl-thiocarbamate and the corresponding sulfinyl carbamate; diphenyl ether and nitrodiphenyl ether: 2,4-dichlorophenyl-4'-nitrophenyl ether [Nitrofen )], 2-chloro-1-(3'-ethoxy-4'-nitrophenoxy)-4-trifluoromethylbenzene [Oxyfluorfen], 2',4'-dichlorophenyl-3-methoxy- 4-Nitrophenyl ether [Chlormethnxinyl], 2-[4′-2″,4″-dichlorophenoxy)phenoxy]-methyl propionate, N-(2′-methoxyethyl)-2 -〔Five'-
(2″-chloro-4″-trifluoromethylphenoxy)phenoxy]propionamide; benzoic acid derivative: 5-(2′,4′-dichlorophenoxy)-2
-Methyl nitrobenzoate, 5-(2'-chloro-
4′-Trifluoromethylphenoxy)-2-nitrobenzoic acid [Acifluorfen], 2,6-dichlorobenzonitrile [Dichlobenil]; Triazines and triazinones: 2,4-bis(isopropyl) amino)-6-methyl-thio-
1,3,5-triazine [Prometryn], 2,4-bis(ethylamino)
-6-methylthio-1,3,5-triazine [Simetryn], 2-(1',2'-dimethylpropylamino)-4-ethylamino-6-methylthio-1,3,5-triazine [ Dimethametryn, 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,
2,4-triazin-5-one [Metribuzin]; Phenyl urea: N-(3'-isopropylphenyl)-N',N'-dimethylurea [Isoproturon], N-(3' , 4′-dimethylbenzyl)-N′-4-tolylurea [Dimuron], N-(3′-chloro-4′-isopropylphenyl)-N′,N′-(3-methyl-pentamethylene -1,5-yl) urea; Nitroaniline: 2,6-dinitro-N,N-dipropyl-4-trifluoromethyl-aniline [Trifluralin], N-(1'-ethylpropyl)-2, 5-dinitro-3,4-xylidine (Pendimethalin); Oxadiazoline: 5-tert-butyl-3-(2',
4′-dichloro-5′-isopropoxyphenyl)—
1,3,4-Oxadiazol-2-one [Oxdiazon]; Pyridyloxyphenoxy derivative: 2-propynyl-2-[4′-(3″,5″-dichloropyridyl-)
2″-oxy)phenoxy]-propionic acid ester; Phosphate: S-2-methylpiperidino-carbonylmethyl-O,O-dipropyl-phosphoro-
Dithioate [Piperophos]; Pyrazole: 1,3-dimethyl-4-(2′,4′-
dichlorobenzoyl)-5-(4'-tolylsulfonyloxy)pyrazole. Phenylpyrimidines of the formula which act as antidotes may optionally be used after or simultaneously with the application of the agrochemical. Many of the phenylpyrimidines of this invention are new, while others are known compounds. Phenylpyrimidines are used as intermediates in the production of dyes and are described, for example, in connection with British Patent No. 1502912 or European Patent Applications Nos. 20298 and 31796. They are known as intermediates for pharmacologically active ingredients: Journal of Medical Chemistry (J.Med.Chem.) (21), pp123
―126; they are also described in the chemical literature: Bulletin de la Societe.
Chimique) Japanese version 44(8), pp2182-5. 2-phenyl-4,6-dichloro- and-
4,6-difluoropyrimidine and a chlorine atom at the 4-position of the phenyl ring, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 3 carbon atoms,
_-COl3 , _-CH2Br , -COOH or _-CH2PO
2-phenyl-4,6-dichloropyrimidine substituted with (OC ₂ H ₅ ) is a known compound. The 3rd position of the phenyl ring is a methyl group, methoxy group, chlorine atom, fluorine atom, nitro group, amino group, CCl ₃ or
those substituted with COOH and the 3rd or 4th position
3,4-dichloro-4-methyl-3- with a pair of positions
Nitro group, 3-chloro-4-methyl group and 4-
Those substituted with an ethoxy-3-nitro group are also known compounds. The new compound is a phenylpyrimidine other than the above-mentioned compounds, in which R ₁ and R ₂ represent a halogen atom in the following formula b. New compounds can be divided into the following subgroups: (In the formula, R ₁ represents a fluorine atom, a bromine atom, or an iodine atom, and R ₃ represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, provided that when R ₁ and R ₃ are fluorine atoms, R It is not a hydrogen atom.) (In the formula, n represents an integer from 1 to 4, and R represents the meaning given in the formula.); (In the formula, R, R ₆ and R ₇ represent the meanings given in the formula, and n represents an integer from 1 to 4.); (In the formula, Z represents R ₅ , NR ₇ R ₈ or OR ₄ , but R ₄ is not a hydrogen atom, and R, R ₄ , R ₅ , R ₇ and R ₈ represent the meaning given in the formula. , and n represents an integer from 1 to 4); (In the formula, each R independently represents the meaning given in the formula excluding a hydrogen atom, and the paired para-meta-dichloro group, para-chloro/
They are a meta-methyl group, a para-methyl/meta-nitro group, and a para-ethoxy/meta-nitro group. ); (In the formula, R represents the meaning given in the formula excluding hydrogen atoms, and n represents an integer from 3 to 5.); (In the formula, R′ is a fluorine atom at the ortho or para position of the pyrimidyl group; a chlorine atom at the ortho position of the pyrimidyl group; a bromine atom, an iodine atom, a trifluoromethyl group, a dichloromethyl group, a chloromethyl group, a difluoro Chloromethyl group, cyano group; -OR ₅ ', -
SR ₅ , ―SOR ₅ , ―SO ₂ R ₅ , ―NR ₆ R ₇ , ―COA,
-CSNR ₆ R ₇ , -SO ₂ NR ₆ R ₇ , -C(OR ₄ ) ₂ R ₄ ,

[Formula] -PO(OR ₄ ) ₂ , -SO ₃ H, -N= CR ₈ R ₉ ; Unsubstituted or substituted alkyl group having 3 to 6 carbon atoms or cycloalkyl group having 3 to 6 carbon atoms; unsubstituted Or - XR ₅ , -
NR ₆ R ₇ , -PO(OR ₄ ) ₂ , -COA or a cyano group substituted with a C 1 -C 6 alkyl group or a C 3 -C 6 cycloalkyl group; or unsubstituted or a halogen atom or - _XR represents an alkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms substituted with R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , A, B and X have the meanings given in the formula, and
R ₅ ' is unsubstituted alkyl having 4 to 6 carbon atoms,
represents an alkenyl group having 3 to 6 carbon atoms or an alkynyl group having 3 to 6 carbon atoms, or a halogen atom, -CO-A, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a C 1 to 6 alkoxy group; represents an alkenylthio group or an alkyl group having 1 to 6 carbon atoms substituted with -NR ₆ R ₇ or an alkenyl group having 3 to 6 carbon atoms, or an alkylcarbonyl group having 2 to 6 carbon atoms; It represents an alkenylcarbonyl group having 3 to 6 carbon atoms or an alkynylcarbonyl group having 3 to 6 carbon atoms. ). Phenylpyrimidines of the formula are obtained by known synthetic procedures. A 2-phenylpyrimidine ring is formed, for example, by condensing phenylamidine with a malonic acid derivative. 2-Phenylpyrimidine can be prepared by mixing phenylamidine with dialkyl malonate in an alcohol solution in the presence of a base using the following formula: 2-phenyl-
Substituting the hydroxyl group of 4,6-dihydroxypyrimidine with a halogenating agent (phosphorooxy chloride, phosphorooxy bromide, sulfuryl chloride, promosuccinimide, etc.) and, if desired, sequentially substituting these halogen atoms with R ₁ and R ₃ You can get it by twisting it. If R ₂ represents a hydrogen atom, these can be replaced, for example, by treatment with chlorine or bromine in a polar solvent, such as glacial acetic acid. The halogen atoms at positions 4, 5 and 6 of the pyrimidine ring can be sequentially substituted with alcohol, mercaptan or amine by known means. For reference, the following publications may be cited, for example: Journal of the Chemical Society (J.Chem.Soc.) 1965 , pp5467-5473; Journal of the Chemical Society (J.Prakt.Chem.). ) 312 (1970), pp494-506; Journal of the Chemical Society, Perkin Trans. 1, 1977 .
pp2285-6. Phenylpyrimidine in which R ₁ represents an alkyl group or a phenyl group can be prepared, for example, by combining phenylamidine with an alkyl ester of acetoacetic acid using the following formula: It can be obtained by condensation as shown below. Here, the hydroxyl group can be substituted with a halogen atom by known means, and in turn can be substituted with an alcohol, thiol or amine. Chlorobenzylidine-carbamoyl chloride is prepared with an aliphatic nitrile in the presence of hydrogen chloride by the following formula: For example, 2-phenyl-4,6-dichloropyrimidine and 2-phenyl-4-chloro-6-hydroxypyrimidine can also be produced by reacting as shown below. Japanese version
44 (1971), pp. 2182–2185. 2-Phenyl-4,6-dichloropyrimidine is, for example, available from Ang.
Chemie) 89 (1977), pp. 816-817, for example, when N-phenyl cyanamide and N,N-dialkylamide are mixed in POCl ₃ at 100°C, the following formula: It can be obtained by condensation as shown below. In each of the above formulas, R, R ₂ and n represent the meanings given in the formulas. The synthesis of these compounds or the transformation of R ₁ , R ₂ and R ₃ with other defined substituents are procedures known per se. Regarding the preparation of these compounds, please refer to the examples or the literature. “The Chemistry of Heterocyclic Compounds”
Compounds)” 16 Interscience (Inter
Science), New York 1962, pp119ff. The compounds of the formula can be used alone or together with compounds to which antagonism is desired. The compounds of the formula can be used in neat form or preferably with the auxiliaries customary in formulation technology and can thus be used as emulsion concentrates, directly sprayable or dilutable solutions, diluted They can be formulated by known methods into dosage forms such as emulsions, wettable powders, soluble powders, dusts or granules, and microencapsulations, for example in polymeric substances. To suit the nature of the composition, the method of application, such as spraying, atomization, dusting, dusting or pouring, is determined depending on the purpose of application and the given situation. The formulations, i.e. compositions or preparations containing the compound of the formula (active ingredient) and optionally suitable solid or liquid auxiliaries, can be prepared by known methods,
For example, they are prepared by homogeneously mixing and/or milling the active ingredient with fillers such as solvents or solid carriers and, if desired, surfactants. Suitable solvents include aromatic hydrocarbons, preferably those having 8 to 12 carbon atoms, such as xylene mixtures or substituted naphthalenes, phthalates such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols. and their ethers and esters such as ethanol, ethylene glycol, monomethyl or monoethyl ether of ethylene glycol, ketones such as cyclohexanone, strongly polar solvents such as N-
Mention may be made of methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized vegetable oils, such as epoxidized coconut or soybean oil, or water. Solid carriers used, for example, for dusts and dispersible powders, usually include natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly dispersed silicic acids or highly dispersed absorbent polymers can also be used to improve the physical properties. Suitable granular adsorptive carriers are porous carriers such as pumice, crushed brick, sepiolite or bentonite, and non-adsorptive carriers are materials such as calcite or sand.
Furthermore, most pre-granulated substances, inorganic or organic, can be used, such as especially dolomites to even powdered plant residues. Suitable surfactants will depend on the nature of the compound represented by the formula to be incorporated, but will have good emulsifying properties,
Nonionic, cationically active and/or anionic surfactants with dispersing and wetting properties.
In this case, surfactants are also understood to mean mixtures of surfactants. Suitable anionic surfactants include water-soluble soaps and water-soluble synthetic surfactant compounds. Soaps that can be used include those with 10 or more carbon atoms.
Alkali metal, alkaline earth metal, or optionally substituted ammonium salts of 22 higher fatty acids, such as the sodium or potassium salts of oleic acid or stearic acid or the sodium or potassium salts of natural fatty acid mixtures obtained from, for example, coconut oil or tallow. can be mentioned. The soap also includes fatty acid methyltaurine salts. However, more often so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. The fatty sulfonates or fatty sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or optionally substituted ammonium salts and contain alkyl radicals having from 8 to 22 carbon atoms, which can also be This meaning includes the alkyl group moiety in the acyl group. Examples include shrimp lignosulfonic acid, dodecyl sulfate or sodium or calcium salts of fatty alcohol sulfates obtained from natural fatty acids. Surfactants of this type also include salts of sulfuric acid esters and fatty alcohol/ethylene oxide adducts of sulfonic acids. The sulfonated benzimidazole derivative preferably has two sulfonic acid groups and 8 carbon atoms.
It has 1 to 22 fatty acid groups. Alkylarylsulfonates include, for example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid-formaldehyde condensation products. Suitable synthetic surfactants also include the corresponding phosphates, such as the salts of the phosphoric acid esters of the adducts of 4 to 14 moles of ethylene oxide with P-nonylphenol. Suitable nonionic surfactants are in particular polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols. The ether derivatives contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon group.
and the alkyl portion of the alkylphenol may contain 6 to 18 carbon atoms. Other suitable nonionic surfactants include polypropylene glycols having 1 to 10 carbon atoms in the alkyl chain, ethylene diamino polypropylene glycols and polyethylene oxide adducts with alkyl polypropylene glycols. This adduct contains 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. This compound usually has 1 to 5 ethylene glycol units per propylene glycol unit. Representative examples of the above nonionic surfactants include:
Nonylphenol polyethoxyethanol, castor oil polyglycol ether, polypropylene/
Mention may be made of polyethyleneoxy adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Suitable nonionic surfactants also include fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan-trioleate. The cationic surfactant has at least one alkyl group having 8 to 22 carbon atoms as an N substituent, and optionally a halogenated lower alkyl group, benzyl group, or lower alkyl hydroxide group as another substituent. Quaternary ammonium salts having the following are preferred. The ammonium salt is preferably in the form of a halide, methyl sulfate or ethyl sulfate, such as stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide. Surfactants commonly used in compounding techniques are described in the following literature: “Mc Cutcheon's Detergent and Emulsifiers Annual.
Detergents and Emulsifers Annual)”, MC Publishing Corporation (Mc
Publishing Corp., Ringewood, New Jersey 1979 edition. “Encyclopedia of SurfS Active Agents”
"Surface Active Agents", Chemical Publishing Co. Inc., New York 1964 edition. The formulation usually contains 0.1 to 99%, preferably 0.1 to 95% of the compound represented by the formula, and a liquid. It contains 1 to 99% additives and 0 to 25% surfactants, preferably 0.1 to 25%. Commercial formulations are preferably formulated as concentrates, but
The end user generally dilutes it before use. The formulations according to the invention can also contain other additives, such as stabilizers, antifoams, viscosity regulators, binders, adhesives and fertilizers or other active ingredients for obtaining special effects. In the following Examples and Reference Examples, parts and percentages are expressed by weight. Production example reference example 1 2-p-tolyl-4,6-bis-isopropoxypyrimidine a Dissolve 21.16 g of sodium metal in anhydrous isopropanol and add 4,6-dichloro-
95.64g of 2-p-tolylpyrimidine from 60 to
Add at 65℃ for at least 15 minutes. The mixture is heated to boiling and refluxed for an additional 4 hours to complete the reaction. Excess isopropanol is distilled off and the residual oil is transferred to chloroform. The chloroform layer was washed with water and dried over sodium sulfate.
pass Next, the solvent is distilled off to obtain 112 g of 2-p-tolyl-4,6-bis-isopropoxypyrimidine as a yellow oil, which is purified by vacuum distillation. The boiling point is 123°C/5.332 Pascals. The starting material, 2-p-tolyl-4,6-dichloropyrimidine, is produced as follows. b p-Tolylamidine hydrochloride
102.3 g and 99.3 g of diethyl malonate are suspended in 520 ml of absolute ethanol. Then add 30% of sodium methylate while stirring and cooling thoroughly.
Add 323.7 g of solution. The reaction mixture is then heated to reflux temperature and stirred at that temperature for 5 hours.
Next, the solvent was distilled off and the residue was transferred to 1000 ml of water.
The solution, which becomes cloudy upon heating to 80°C, is filtered over silica gel. Cool the liquid and acidify with 15% hydrochloric acid. The thick crystal slurry is filtered, the residue is washed with water, and dried at 100°C to obtain 100 to 110 g of 2-p-tolyl-4,6-hydroxypyrimidine having a melting point of 314°C (with decomposition). c 72.6 g of dihydroxy compound, 72.6 g of N,N-dimethylaniline and 363 g of phosphorus oxychloride
Boil the mixture at reflux temperature for 1 hour.
Stir for an hour. Excess phosphorus oxychloride is distilled off, and the residue is washed with ice water to remove any remaining phosphorus oxychloride and filtered with ice water. Wash the excess residue with ice water,
Vacuum drying at 40 to 50℃, melting point 86 to 87℃
85.9 g of 2-p-tolyl-4,6-dichloropyrimidine was obtained. Reference example 2 2-p-tolyl-4,6-bis-isopropoxy-5-bromopyrimidine 70 to 75 g of 4,6-diisopropoxy-2-p-tolylpyrimidine and 450 ml of carbon tetrachloride
Heat to ℃. Add dibenzoyl peroxide to this solution.
Add 0.5g of azoisobutyronitrile and 1g of N
-Add the mixture with 70.8 g of bromosuccinimide over 45 minutes. The mixture is refluxed for 2 hours to complete the reaction. The precipitated succinimide is separated and excess carbon tetrachloride is removed by distillation to determine the melting point.
141 g of the title compound are obtained at 74-75°C (after methanol purification). Reference example 3 2-p-tolyl-4,6-dimethoxypyrimidine 156.1 g of a 30.5% solution of sodium methylate is stirred with 700 ml of absolute methanol. Next, add 2-p-tolyl-4,6-dichloropyrimidine to this solution for at least 10 minutes and while cooling it secretly.
Add 95.64g. Heat the mixture to reflux and continue boiling for 4 hours. The solvent is removed by distillation and the residue is transferred into 1000 ml of water. Poke the product while still containing water to remove sodium chloride,
Filtration, separation, washing with water and drying in air give 90.4 g of the title compound, melting point 61-62°C. Reference example 4 2-p-chlorophenyl-4,6-dihydroxypyrimidine A 30% methanolic solution of sodium methylate in a suspension of 38.2 g of 4-chlorobenzylamidine and 33.6 g of diethylmalonate in 175 ml of methanol 108
g over 10 minutes and refluxed for 5 hours. The solvent is distilled off in a rotary evaporator, the residue is transferred to 1000 ml of hot water and the solution is filtered. When the liquid is acidified to PH1, the precipitate is filtered and separated, and dried under vacuum at 80°C, 2-p-chlorophenyl with a melting point of 333°C (decomposition) is obtained.
44 g of 4,6-dihydroxypyrimidine are obtained. Reference example 5 2-p-chlorophenyl-4,6-dichloropyrimidine 50 ml of phosphorus oxychloride (POCl ₃ ) is added dropwise to 22 ml of N,N-dimethylaniline at room temperature. Next 2-p
Add 22.3 g of -chlorophenyl-4,6-dihydroxypyrimidine in portions while cooling to keep the temperature below 40°C. After stirring the reaction mixture for 2 hours at room temperature, it is refluxed for 2 hours and then concentrated by rotary evaporation. Scrape the residue with 500 ml of water and suction. The percake is dissolved in methylene chloride and the solution is treated with acid clay, dried and concentrated. The residue crystallizes, melting point 119-120°C
16.2 g of 2-p-chlorophenyl-4,6-dichloropyrimidine was obtained. Samples sublimated at 80°/0.02 mbar melt at 120-121°C. Reference example 6 2-p-methoxyphenyl-4,6-dihydroxypyrimidine To a suspension of 112 g of p-methoxybenzamidine hydrochloride and 101 g of diethyl malonate in 520 ml of ethanol is added 338 g of a 30% methanol solution of sodium methylate over 10 minutes, followed by refluxing for 5 hours. The reaction mixture is concentrated in a rotary evaporator and the residue is dissolved in 1000 ml of hot water at 80°C. Filter the solution and acidify the solution to PH1. filtrate the precipitate,
Separate and vacuum dry at 80℃ to obtain a melting point of 318℃ (decomposition)
109.8 g of 2-p-methoxyphenyl-4,6-dihydroxypyrimidine was obtained. Reference example 7 2-p-methoxyphenyl-4,6-dichloropyrimidine 126 ml of phosphorus oxychloride (POCl ₃ ), then N,
57ml of N-dimethylaniline to 54.5g of 2-p-methoxyphenyl-4,6-dihydroxypyrimidine
Add the mixture dropwise over 30 minutes while cooling it so that the temperature does not exceed 45℃. The reaction mixture is then concentrated on a rotary evaporator and the residue is triturated in 2 liters of ice water. The solid product is filtered off, dissolved in 1.5 liters of methylene chloride and the solution is treated with acid clay and dried. Filter and concentrate the methylene chloride solution.
The residue was recrystallized from ethanol to give 2-p-methoxyphenyl-4,6- with a melting point of 127-128°C.
51 g of dichloropyrimidine are obtained. The following compound is produced by a method similar to that described in the above reference example.

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[Table] Example of formulation Normally, the compound represented by the formula is not used alone in agriculture. They can be used directly or diluted with water and are used in ready-to-use formulations. Reference Example 8 Powder: The following materials are used to formulate a) 5% powder and b) 2% powder. a Mixture with 2-p-tolyl-4,6-bisisopropoxypyrimidine or 2-chloro-2',6'-diethyl-N-(butoxymethyl)-acetanilide 5 parts Talc 95 parts b The above active ingredients or Mixture 2 parts highly dispersed silicic acid 1 part talc 97 parts The above active ingredients are mixed with a carrier, ground and used in this form as a powder. Reference Example 9 Granules: The following materials are used to formulate 5% granules. 2-p-tolyl-4,6-isopropoxy-5
-Promopyrimidine or 2-chloro-2',6'-
Mixture with diethyl-N-(methoxymethyl)-acetanilide 5 parts epoxidized vegetable oil 0.25 parts cetyl polyglycol ether 0.25 parts polyethylene glycol 3.25 parts kaolin (particle size 0.3-0.8 mm) 91 parts The above active ingredient or mixture with vegetable oil Mix and dissolve the mixture in 6 parts of acetone, then add polyethylene glycol and ether. The solution thus obtained is sprayed onto kaolin and the acetone is evaporated in vacuo. Microgranular formulations of this type are convenient for use in combination with sowing fields. Reference example 10 Hydrating agent: a) 70% hydrating agent, b) 40% hydrating agent,
The following ingredients are used to formulate c) 25% hydrating agent, d) 25% hydrating agent and e) 10% hydrating agent. a 2-p-tolyl-4,6-bis-(methoxyethyl)-5-chloropyrimidine or 2-chloro-2',6'-diethyl-N-(2''-propoxyethyl)-acetanilide 70 parts dibutylnaphthalene Sodium sulfonate 5 parts Naphthalenesulfonic acid/phenolsulfonic acid/formaldehyde condensate (3:2:1)
3 parts kaolin 10 parts Champagne chalk
12 parts b Active ingredient or mixture as described above 40 parts Sodium lignosulfonate 5 parts Sodium dibutylnaphthalene sulfonate 1 part Silicic acid 54 parts (1:1) 1.9 parts sodium dibutylnaphthalene sulfonate
1.5 parts Silicic acid 19.5 parts Yang punch yoke 19.5 parts Kaolin 28.1 parts d Active ingredients or mixtures of the above 25 parts Isooctylphenoxypolyethylene ethanol 2.5 parts Yang punch yoke/Hydroxyethyl cellulose mixture (1:1) 1.7 parts Sodium aluminum silicate 8.3 parts diatomaceous earth 16.5 parts kaolin 46 partse Active ingredients or mixtures of the above 10 parts Sodium salt mixture of saturated fatty alcohol sulfates 3 parts Naphthalene sulfonic acid/formaldehyde condensate 5 parts Kaolin 82 parts Add with active ingredients in a suitable mixer Mix thoroughly and grind with suitable grinders and rollers. A wettable powder having excellent wetting and suspending properties is obtained. These wettable powders can be diluted with water to give suspensions of the desired concentration and can be used in particular for foliar spraying for growth prevention or weed control. Reference example 11 Concentrated emulsion: The following substances are used to formulate a 25% concentrated emulsion. 2-phenyl-4-chloro-6-methylpyrimidine or 2-chloro-6′-ethyl-N-(2″-
Methoxy-1″-methylethyl)-acet-O-
Toluidide 25 parts Epoxidized vegetable oil 2.5 parts Alkylaryl sulfonate/fatty alcohol polyglycol ether mixture 10 parts Dimethylformamide 5 parts Xylene 57.5 parts Reference Example 12 Paste: The following materials are used to formulate the 45% paste. a Mixture with 2-phenyl-4-chloro-6-hydroxypyrimidine or 2-chloro-2',6'-diethyl-N-(methoxymethyl)-acetanilide 45 parts Sodium aluminum silicate 5 parts b The above active ingredients or Mixture 45 parts ethylene glycol 5 parts octylphenoxy polyethylene glycol (containing 9 to 10 moles of ethylene oxide per mole of octylphenol) 3 parts mixture of aromatic sulfonic acid ammonium salts condensed with formaldehyde 3 parts silicone oil (75% emulsion) ) 1 part 1-(3-chloroallyl)-3,5,7-triazo-azonium-adamantane chloride mixture with soda carbonate (chlorine value of at least 11.5%)
0.1 part biopolymerization thickener (contains up to 100 pachylus/g)
0.2 parts water 42.7 parts Mix the active ingredient and auxiliary agent uniformly in a suitable device,
Smash. By diluting the paste thus obtained with water, a suspension of the desired concentration is obtained. Biological Testing Examples It is seen in the examples below that the compounds of the formula have the ability to protect cultivated plants from the phytotoxic effects of powerful herbicides. In the test prescription,
The compound represented by the formula is called an antidote and the protective effect is expressed in %. 0% indicates the herbicidal effect when only the herbicide is used; 100% indicates the expected normal growth of the cultivated plants. A protective effect of at least 10% is significant. The numbered antidote compounds used in the following examples and reference examples are the same as the numbered antidote compounds described on pages 97 to 127 of the specification. Example 1 Test using antidote and herbicide in transplanted rice Method of use: Tank mixture Rice seedlings are cultivated in soil to about 1.5 to 2 leaves. The seedlings are then tied up in bundles (usually three in a bundle) and transplanted into sand-filled clay in a 47cm x 29cm x 24cm container. Cover the soil surface with water to a height of 1.5 to 2 cm. Two to three days after transplanting, the test herbicide and antidote are added together as a tank mixture directly to the water. The protective effect of the antidote is evaluated as a percentage 24 days after transplantation. Seedlings treated with herbicides only (no protective treatment) and controls that were not treated at all (100% growth rate) serve as a reference for evaluation. The results are reported below.

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[Table] Similarly, rice plants are protected from the phytotoxic effects of S-benzyl-N,N-diethylthiocarbamate. Example 2 Test using antidote and herbicide in transplanted rice Method of use: Root treatment Yamabiko rice seedlings are grown in the soil to about 1.5 to 2 leaves and washed with water. Only the roots of a bunch of seedlings (usually in bundles of three) are placed in a dish containing a solution with a concentration of 1000 ppm of the compound to be tested as an antidote.
Soak for 15 to 60 minutes. Next, transfer the seedlings to sand-filled clay in a 47 cm x 29 cm x 24 cm container and cover the soil surface with water to a height of 1.5 to 2 cm. After transplant 2
After 3 days, the herbicide is added directly to the water. The protective effect of the antidote is evaluated as a percentage 24 days after transplantation. Seedlings treated with herbicides only (no protective treatment)
and a control that was not treated at all (100% growth rate)
will serve as a reference for evaluation. The results are reported below.

[Table] Example 3 Tests using antidotes and herbicides on transplanted rice seedlings.
Use of antidotes on rice seedlings with aqueous solutions (drench method). Seedlings of Yamabiko rice in a seeding dish at 1.5 to 2
Cultivate to the point of leaves. One to two days before transplanting, the seeding dish is immersed together with the rice seedlings in a larger dish containing a solution of the compound to be tested as an antidote at a concentration of 1000 ppm. Next 47cm x 29cm x
Transplant the seedlings into sand-filled clay in a 24 cm container.
Cover the soil surface with water to a height of 1.5 to 2 cm.
The herbicide is added directly to the water 2 to 3 days after transplanting. The protective effect of the antidote is evaluated as a percentage 24 days after transplantation. Seedlings treated with herbicides only (no protective treatment) and controls that were not treated at all (growth rate
100%) will serve as a reference for evaluation. The results are reported below.

[Table] Example 4 Tests using antidotes and herbicides in transplanted rice. Pre-emergence use of antidotes. The compound used as an antidote is sprayed in the form of a dilute solution over substantially the entire surface of the soil in the seeding dish. Next, the rice seeds are sown in a dish and cultivated until they reach 11/2 to 2 leaves. Next, transplant the seedlings in bundles (usually 3 plants in a bundle) into sand-filled clay in a 47 cm x 29 cm x 24 cm container, and cover the soil surface with water to a height of 1.5 to 2 cm. Apply herbicide directly 2 to 3 days after transplanting.
Add to water. The protective effect of the antidote is evaluated as a percentage 24 days after transplantation. Seedlings treated with herbicides only (no protective treatment) and controls that were not treated at all (100% growth rate) serve as a reference for evaluation. The results are reported below.

[Table] Example 5 Tests using antidotes and herbicides in transplanted rice. Precultivation application method. The compound to be tested as an antidote is applied to the soil in the seeding tray at a concentration of 100 ppm. After two days, the rice seedlings will grow to 11/2 to 2 leaves in the treated seeding tray.
Next, transplant the seedlings in bundles (usually three in a bundle) into sand-filled clay in a 47cm x 29cm x 24cm container, and cover the soil surface with water to a height of 1.5 to 2cm. The herbicide is added directly to the water 2 to 3 days after transplanting. The protective effect of the antidote is evaluated as a percentage 24 days after transplantation. Seedlings treated with herbicides only (no protective treatment) and controls that were not treated at all (100% growth rate) serve as a reference for evaluation. The results are reported below.

[Table] Example 6 Tests using antidotes and herbicides in transplanted rice. Post-emergence application of antidote (from above the tips of the rice plants). Cultivate Yamabiko rice seedlings in the soil until they reach 11/2 or 2 leaves. The compound to be tested as an antidote is then sprayed onto the rice seedlings in the form of a dilute solution. 47cm after 2 days
Transplant the rice in bundles (usually 3 plants in a bundle) into sand-filled clay in a 29 cm x 24 cm container and cover the soil surface with water to a height of 1.5 to 2 cm. The herbicide is added directly to the water 2 to 3 days after transplanting. The protective effect of the antidote is evaluated as a percentage 24 days after transplantation. Seedlings treated with herbicides only (no protective treatment) and controls that were not treated at all (growth rate
100%) will serve as a reference for evaluation. The results are reported below.

[Table] The 2-phenylpyrimidines of the present invention used in the test methods described in Examples 13 to 18 also showed the effects on transplanted rice when the following herbicides were used in place of the above herbicides: Indicates the protective effect of species:
S-2-Methyl-piperidino-carbonylmethyl-0,0-dipropyl-phosphorodithioate {“Piperophos”}, S-ethyl-
N,N-hexamethylene thiocarbamate {“Molinate”}, S-4-chlorobenzyl-diethyl-thiocarbamate {“Thiobencarb”}, S-4-benzyl-diethyl-thiocarbamate, 5 -Tertiary-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)1,3,4-oxa-diazole-2
-ON {“Oxadiazon”} or N-(3,4-dichlorophenyl-propionamide {“Propanil”}) Example 7 Antidote and herbicide tests on submerged rice. (Soak rice seeds and sow directly into very moist, swampy or flooded soil.) Soak rice seeds in water for 48 hours. 25cm x 17cm x 12cm.
Fill the plastic container with soaked seed soil. The compound to be tested as an antidote and herbicide are sprayed as a tank mixture onto the soil surface. Gradually raise the water level as the rice seedlings grow. The protective effect of the antidote is evaluated in percentage after 21 days. Seedlings treated with herbicide only (no protective treatment) and controls that were not treated at all (growth rate 100
%) will serve as a reference for evaluation. The results are reported in the table below.

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Table: The antidote, namely Compound No. 1, as well as other 2-phenylpyrimidines of the invention, also contains 3-4-benzyl-diethylthiocarbamate and 5-tert-butyl-3-(2,4- Dichloro-5-isopropoxyphenyl)-1,3,4-oxodiazol-2-one “Oxdiazon”
was able to protect rice plants from phytotoxicity. Example 8 Antidote and herbicide tests on soaked rice seeds. Use of antidotes during soaking of rice seeds. Rice seeds are soaked in an antidote solution with a concentration of 100 ppm for 48 hours. The seeds were then allowed to dry for approximately 2 hours until no longer sticky. 25cm x 17cm x 12cm
Fill a plastic container with sand to a depth of 2 cm below the rim. Sow the soaked seeds on the soil surface in the container and cover very lightly with soil. Keep the soil mixed (not mushy). A dilute solution of herbicide is then sprayed onto the soil surface. Gradually raise the water level as the seedlings grow. The protective effect of the antidote is evaluated in percentage after 21 days. Seedlings treated with herbicides only (no protective treatment) and controls that were not treated at all (100% growth rate) serve as a reference for evaluation. The results are reported in the table below.

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[Table] Rice also contains S-benzyldiethylthiocarbamate and 5-tert-butyl-3-(2,4-
dichloro-5-isopropoxyphenyl)-1,
3,4-Oxydiazol-2-one “Oxdiazon” Example 9 Test with antidote and herbicide on submerged rice. Use of antidotes and herbicides in culture fluids. Seeds that would normally be damaged by the herbicide at the test concentration are sown in granular Zonolith (foamed vermiculite) in plastic flower pots (top diameter 6 cm) with holes in the bottom. Each pot is then placed in a second transparent plastic flower pot (top diameter 7 cm) containing approximately 50 ml of culture solution prepared with herbicide and antidote. This medium rises by capillary action through the material filling the small pot, moistening the seeds and germinated plants. Replenish the lost medium daily with 50 ml of Hewitt medium. The protective effect is evaluated in % three weeks after the start of the test. Seedlings treated with herbicides only (no protective treatment) and controls that were not treated at all (100% growth rate) serve as a reference for evaluation. The results are reported below.

[Table] Example 10 Test using antidote and herbicide on soaked and dried seedlings (20 days after soaking, when rice seedlings reach three leaves, flooded soil). Use of antidotes and herbicides as tank mixtures. Sow IR-36 rice seeds in a 47cm x 29cm x 24cm container, cover with soil and gently tamp down. The antidote and herbicide to be tested are sprayed onto the soil as a tank mixture. 20 days after sowing, when the rice seedlings have about three leaves, cover the soil surface with water to a height of 4 cm. Evaluate the protective effect of the antidote in % on the 30th day after transplantation. Seedlings treated with herbicides only (no protective treatment) and controls that were not treated at all (100% growth rate) serve as a reference for evaluation. The results are reported in the table below.

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[Table] Example 11 Tests with antidotes and herbicides in dry rice. Use of antidote by seed dusting. IR-36 rice seeds are mixed with the test antidote in a glass container. Thoroughly mix the seeds and test compound by shaking and rotating. Dimensions: 47cm x 29cm
Fill a 24cm x 24cm container with sand-filled clay and sow the sprinkled seeds inside. Cover the seeds with soil and then spray the herbicide on the soil surface. The protective effect of the antidote is evaluated in percentages 18 days after sowing. Seedlings treated with herbicides only (no protective treatment) and controls that were not treated at all (100% growth rate) serve as a reference for evaluation. The results are reported below.

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[Table] Example 12 Tests with antidotes and herbicides on soybeans. Pre-emergence application of tank mixtures of antidotes and herbicides. A flower pot with a diameter of 6 cm at the top is filled with sand-filled clay and soybean seeds of the Hark variety are sown in it. The seeds are covered with soil and then a dilute solution of the test antidote is sprayed onto the soil surface in a tank mix along with the herbicide. The protective effect is evaluated in percent 21 days after herbicide application. Plants treated with herbicide only (no protective treatment) as well as controls that were not treated at all (100% growth rate) serve as a reference for the evaluation. The results are shown below.

[Table] Example 13 Tests with antidotes and herbicides on sorghum.
Pre-emergence application of tank mix of antidote and herbicide. Fill a flower pot with a diameter of 6 cm at the top end with sand-filled clay, and sow sorghum seeds of the “Fank G522” variety. The seeds are covered with soil and a tank mixture of a dilute solution of the test antidote and herbicide is sprayed onto the soil surface. The protective effect is evaluated in percent 14 days after herbicide application. Plants treated with herbicide only (no protective treatment) as well as controls that were not treated at all (100% growth rate) serve as a reference for the evaluation. The results are shown below.

[Table] Example 14 Tests with antidotes and herbicides in wheat. Pre-emergence application of tank mix of antidote and herbicide. In a greenhouse, wheat seeds are sown in plastic pots containing 0.5 liters of field soil. Seedlings with about 2 to 3 leaves after germination are then treated with a tank mixture of test antidote and herbicide. Evaluate the protective effect of the antidote in percentages 20 days after use. Plants treated with herbicide only (no protective treatment) as well as controls that were not treated at all (100% growth rate) serve as a reference for the evaluation. The results are shown below.

[Table] Example 15 Tests with antidotes and herbicides on cereals. Pre-emergence application of tank mixtures of antidotes and herbicides. In a greenhouse, wheat or barley seeds are sown in plastic pots with a top diameter of 11 cm and containing 0.5 liters of field soil. The seeds are covered with soil and a tank mixture of a dilute solution of the test antidote and herbicide is sprayed onto the soil surface. The protective effect is evaluated in percent 24 days after herbicide application. Plants treated with herbicide only (no protective treatment) as well as controls that were not treated at all (100% growth rate) serve as a reference for the evaluation. The results are shown below.

[Table] Example 16 Tests with antidotes and herbicides on corn. Pre-emergence application with tank mix of antidote and herbicide. Seeds of “LG5” corn are sown in plastic pots with a diameter of 11 cm at the top and 0.5 liters of field soil in a greenhouse. The seeds are covered with soil and a tank mixture of a dilute solution of the test antidote and herbicide is sprayed onto the soil surface. The protective effect is evaluated in percent 18 days after herbicide application. Plants treated with herbicide only (no protective treatment) as well as controls that were not treated at all (100% growth rate) serve as a reference for the evaluation. The results are shown below.

[Table] Example 17 Tests with antidotes and herbicides on corn. Use of antidote by seed dusting. “LG5” corn seeds are mixed with the test antidote in a glass container. Thoroughly mix the seeds and compound by vibration and rotation. Fill a plastic pot with a diameter of 11 cm at the top end with field soil, and sow the sprinkled seeds in it. Cover the seeds with soil and apply herbicides before germination. The protective effect is evaluated in percent 18 days after herbicide application. Plants treated with herbicide only (no protective treatment) as well as controls that were not treated at all (100% growth rate) serve as a reference for the evaluation. The results are shown below.

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Claims (1)

[Claims] 1. As an antidote, the following formula: (In the formula, n represents an integer of 0, 1, 2 or 3, R ₁ and R ₃ each independently represent a halogen atom, R ₂ represents a hydrogen atom, R is a halogen atom, a nitro group, Cyano group, -
XR ₅ , ―NR ₆ R ₇ , ―CO―R ₄ , ―CONR ₆ R ₇ , ―
SO ₂ --NR ₆ R ₇ , --SO ₃ H, unsubstituted or halogen atom, --OR ₅ , --NR ₆ R ₇ , --CO--R ₄ or alkyl having 1 to 6 carbon atoms substituted with cyano group, represents a cycloalkyl group having 3 to 6 carbon atoms, an unsubstituted or halogen-substituted alkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms; , R ₄ represents a hydrogen atom, unsubstituted or halogen atom-substituted alkyl having 1 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms, or alkynyl group having 2 to 6 carbon atoms, and R ₅ represents R ₄ , and in addition represents an alkylcarbonyl group having 1 to 6 carbon atoms, R ₆ and R ₇ each independently represent a hydrogen atom or an alkenyl group having 3 to 6 carbon atoms, or Either R ₆ or R ₇ is - CO
-R ₄ or -OR ₄ group or -CONR ₆ R ₇ group, X is oxygen atom, sulfur atom, -SO- or -
SO ₂ - represents. 1. A composition for protecting cultivated plants from the phytotoxic effects of herbicides, the composition comprising a phenylpyrimidine represented by the following formula together with a suitable carrier. 2. The composition according to claim 1, wherein the cultivated plants are cereals, rice, corn, sorghum, and soybean. 3. The composition of claim 1, wherein the antidote is 2-phenyl-4,6-dichloropyrimidine. 4 The antidote is 2-(4'-chlorophenyl)-
The composition according to claim 1, which is 4,6-dichloropyrimidine. 5 The antidote is 2-(4'-methoxyphenyl)
The composition according to claim 1, which is -4,6-dichloropyrimidine. 6. The composition according to claim 1, further comprising a herbicide. 7. The composition according to claim 6, wherein the herbicide is chloroacetanilide. 8. The composition according to claim 6, wherein the herbicide is a carbamate, thiocarbamate or sulfinyl carbamate. 9. The composition according to claim 6, wherein the herbicide is diphenyl ether or nitrophenyl ether. 10. The composition according to claim 6, wherein the herbicide is a benzoic acid derivative. 11. The composition according to claim 6, wherein the herbicide is triazine or triazinone. 12. The composition according to claim 6, wherein the herbicide is nitroaniline. 13. The composition according to claim 6, wherein the herbicide is an oxadiazolone. 14. The composition according to claim 6, wherein the herbicide is a pyridyloxyphenoxy derivative. 15. The composition according to claim 6, wherein the herbicide is a phosphoric acid derivative. 16. The composition according to claim 6, wherein the herbicide is chloroacetanilide. 17. The composition according to claim 6, wherein the herbicide is 2-chloro-2',6'-diethyl-N-2',6'-diethyl-N-(2''-propoxyethyl)acetanilide. 18. The composition according to claim 6, wherein the herbicide is 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide. 19. The herbicide is 2-chloro-2'. , 6'-diethyl-N-(methoxymethyl)acetanilide. 20. The herbicide is 2-chloro-6'-ethyl-N-
-(2″-methoxy-1″-methylethyl)acetate-
The composition according to claim 6, which is o-toluidide. 21 The herbicide is 2-chloro-6'-ethyl-N
The composition according to claim 6, which is -(2'-propoxy-1-methylethyl)aceto-o-toluidide. 22 The herbicide is 2-chloro-6'-ethyl-N
(2-butoxy-1-methylethyl)aceto-o
- The composition according to claim 6, which is toluidide. 23. The composition according to claim 6, wherein the herbicide is S-2-methyl-piperidinocarbonylmethyl-O,O-dipropylphosphorodithioate. 24. The composition according to claim 6, wherein the herbicide is S-4-chlorobenzyl-diethylthiocarbamate. 24. The composition of claim 6, wherein the herbicide is S-4-benzyl-diethylthiocarbamate. 26 The herbicide is chloroacetanilide and the antidote is 2-phenyl-4,6-
7. The composition according to claim 6, which is dichloropyrimidine. 27 The herbicide is chloroacetanilide and the antidote is 2-(4'-tolyl)-
The composition according to claim 6, which is 4,6-dichloropyrimidine. 28 The herbicide is chloroacetanilide and the antidote is 2-phenyl-4,6-
7. The composition of claim 6, which is dibromopyrimidine. 29 The herbicide is chloroacetanilide and the antidote is 2-(2'-tolyl)-
The composition according to claim 6, which is 4,6-dibromopyrimidine. 30 The herbicide is 2-chloro-6'-ethyl-N
-(2″-methoxy-1″-methylethyl)acetate-
o-toluidine, and the antidote is 2-
The composition according to claim 6, which is phenyl-4,6-dichloropyrimidine. 31 The herbicide is 2-chloro-2′,6′-diethyl-N-(2″-propoxyethyl)acetanilide, and the antidote is 2-phenyl-
The composition according to claim 6, which is 4,6-dichloropyrimidine. 32 The herbicide is 2-chloro-2′,6′-diethyl-N-(2″-propoxyethyl)acetanilide, and the antidote is 2-(p-tolyl)-4,6-dichloropyrimidine. The composition of claim 6. 33. The herbicide is 2-chloro-6'-ethyl-N.
-(2″-methoxy-1″-methylethyl)acetate-
o-toluidine, and the antidote is 2-
The composition according to claim 6, which is (p-tolyl)-4,6-dichloropyrimidine.